WO2010119708A1 - Thiol-containing liquid rubber composition - Google Patents

Thiol-containing liquid rubber composition Download PDF

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Publication number
WO2010119708A1
WO2010119708A1 PCT/JP2010/002794 JP2010002794W WO2010119708A1 WO 2010119708 A1 WO2010119708 A1 WO 2010119708A1 JP 2010002794 W JP2010002794 W JP 2010002794W WO 2010119708 A1 WO2010119708 A1 WO 2010119708A1
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Prior art keywords
styrene
thiol
mass
rubber composition
liquid rubber
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PCT/JP2010/002794
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French (fr)
Japanese (ja)
Inventor
北野　創
秀洋 赤間
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株式会社ブリヂストン
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Application filed by 株式会社ブリヂストン filed Critical 株式会社ブリヂストン
Priority to EP10764294.4A priority Critical patent/EP2420535A4/en
Priority to JP2011509228A priority patent/JP5653344B2/en
Priority to CN201080027163.9A priority patent/CN102459447B/en
Priority to US13/264,666 priority patent/US8865841B2/en
Publication of WO2010119708A1 publication Critical patent/WO2010119708A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols

Definitions

  • the present invention relates to a thiol-containing liquid rubber composition excellent in curability in which a liquid styrene-butadiene copolymer and a specific polythiol are blended.
  • rollers such as developing rollers, charging rollers, and transfer rollers used in printers and copiers, blades such as developing blades and cleaning blades, gasket members, display sealing materials, and architectural sealing materials.
  • a rubber composition using a rubber-based resin such as a styrene-butadiene copolymer is employed.
  • a curing treatment is performed by adding a thiol-based crosslinking agent such as a triazine thiol compound (see Patent Document 1).
  • thiol-based crosslinking agents have polarity, they are not compatible with rubber-based resins such as styrene-butadiene copolymers, and when photocured or thermally cured due to poor solution uniformity. There is a possibility that an uncured portion may be formed or phase separation may occur, resulting in poor storage stability. Since such a phenomenon may cause the composition to become opaque, in particular, in the case of photocuring, there is a possibility that the light transmittance is deteriorated and the internal curing becomes insufficient.
  • an object of the present invention is to provide a rubber composition having improved curability by improving compatibility with a thiol-based crosslinking agent while employing such a styrene-butadiene copolymer.
  • the present inventors have found a thiol-containing liquid rubber composition containing a specific styrene-butadiene copolymer and polythiol, and have completed the present invention.
  • the thiol-containing liquid rubber composition of the present invention is A styrene-butadiene copolymer (A) which is liquid at 25 ° C .; And a polythiol (B) derived from mercaptocarboxylic acid.
  • the styrene-butadiene copolymer (A) preferably has a bound styrene content of 20 to 90% by mass, and is preferably a random copolymer.
  • the polythiol (B) includes tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, penta Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) And at least one selected from the group consisting of 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Preferably there is.
  • the content of the polythiol (B) may be 40 parts by mass or less with respect to 100 parts by weight of the styrene-butadiene copolymer (A).
  • the number average molecular weight (Mn) of the styrene-butadiene copolymer (A) is preferably 1200 to 40000.
  • the compatibility between the styrene-butadiene copolymer as a rubber resin and the polythiol (B) as a crosslinking agent is extremely excellent, and due to the nonuniformity of the solution.
  • production of an unhardened part can be avoided.
  • production of an unhardened part can be reduced effectively, even if it is any of photocurability and thermosetting, favorable sclerosis
  • rollers such as developing rollers, charging rollers, and transfer rollers used in printers and copying machines, blades such as developing blades and cleaning blades, and gaskets. It is useful in a wide range of applications such as members, sealing materials for displays, and sealing materials for buildings.
  • the thiol-containing liquid rubber composition of the present invention is A styrene-butadiene copolymer (A) which is liquid at 25 ° C .; It contains polythiol (B) derived from mercaptocarboxylic acid, and an initiator or the like used for photocuring or thermosetting can be added as necessary.
  • the styrene-butadiene copolymer (A) used in the thiol-containing liquid rubber composition of the present invention is liquid at 25 ° C. (room temperature).
  • diene rubbers such as butadiene rubber and isoprene rubber are non-polar, and thus have poor compatibility with polar compounds such as thiol cross-linking agents.
  • polar compounds such as thiol cross-linking agents.
  • the styrene-butadiene copolymer is similarly nonpolar. In spite of this, the compatibility becomes good and the mixing operation of these components becomes easy.
  • the method for producing the styrene-butadiene copolymer (A) is not particularly limited, and can be obtained by copolymerizing a monomer that is 1,3-butadiene and a styrene monomer.
  • a lithium-based polymerization initiator can be used for the copolymerization, and a randomizer or the like may be used as necessary.
  • anionic polymerization is performed using a lithium-based polymerization initiator, it is also possible to optionally modify the living terminal of the polymer chain with various modifiers. For example, by using an alkylene oxide such as ethylene oxide or propylene oxide as a modifier, a diene polymer having hydroxyl groups at both ends or one end can be obtained.
  • the arrangement of the monomers in the copolymer in the styrene-butadiene copolymer (A) is not particularly limited, and is a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. Any of them may be used, but a random copolymer is preferable. If it is a random copolymer, unsaturated groups will be arranged more randomly in the copolymer, which can contribute to improved compatibility with polythiol (B) and further to improved heat resistance of the cured product. .
  • an ether such as tetrahydrofuran or a randomizer such as 2,2-bis (tetrahydrofuryl) propane may be added for polymerization.
  • the styrene-butadiene copolymer (A) has a number average molecular weight (Mn) of 1200 to 40000, preferably 3000 to 30000.
  • Mn number average molecular weight
  • the physical properties such as the strength and elongation are good, and when it is 40000 or less, the compatibility with the polythiol, or the viscosity Due to this problem, the processability at the time of molding is also good.
  • the styrene-butadiene copolymer (A) has a bound styrene content of 90% by mass or less, preferably 25 to 65% by mass.
  • the vinyl bond content of the butadiene moiety is 20 to 85%, preferably 25 to 80%.
  • the styrene-butadiene copolymer (A) preferably has hydroxyl groups at both ends or one end.
  • the compatibility with polythiol is further improved.
  • the polythiol (B) used in the thiol-containing liquid rubber composition of the present invention is a polythiol derived from mercaptocarboxylic acid, and preferably a polythiol derived from 3-mercaptopropionic acid.
  • the polythiol (B) preferably has a plurality of mercaptoacyloxy groups in the molecule, more preferably 2-6.
  • the mercaptoacyloxy group specifically, 3-mercaptopropionyloxy group [HS— (CH 2 ) 2 —COO—], 3-mercaptobutyloxy group [HS—CH (CH 3 ) —CH 2- COO-] and the like, and a 3-mercaptopropionyloxy group is preferable.
  • the mercaptocarboxylic acid-derived polythiol (B) is blended with, for example, a thermal radical generator, a thiyl radical is generated by the radical derived from the thermal radical generator, and the thiyl radical is converted into the styrene-butadiene copolymer (A). Adding to the unsaturated bond promotes the curing (crosslinking) reaction.
  • polythiol (B) examples include tetraethylene glycol bis (3-mercaptopropionate) represented by the following chemical formula (I) and trimethylolpropane tris (3-mercaptoprote represented by the following chemical formula (II).
  • the polythiol (B) has a high compatibility with the styrene-butadiene copolymer (A), and a uniform and stable composition can be obtained.
  • these polythiol (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the polythiol (B) is not particularly limited, but is preferably in the range of 40 parts by mass or less with respect to 100 parts by mass of the styrene-butadiene copolymer (A), and 3 to 35 parts by mass. The range of 5 to 30 parts by mass is even more preferable. If the blending amount of the polythiol (B) is 40 parts by mass or less, good compatibility with the liquid rubber can be maintained, and if it is 3 parts by mass or more, the light or thermosetting property of the composition is sufficiently improved. This is desirable.
  • the thiol-containing liquid rubber composition of the present invention contains a so-called diene polymer other than the above styrene-butadiene copolymer (A) as long as it does not impair the object of the present invention. May be.
  • diene polymer examples include natural rubber, polyisoprene, polybutadiene, butadiene-isoprene copolymer, isobutylene-isoprene copolymer, butadiene-acrylonitrile copolymer, styrene-isoprene copolymer, and polychloroprene. It is done.
  • the terminal of these diene polymers may be modified or may not be modified.
  • a photopolymerization initiator may be blended.
  • photopolymerization initiators include benzoin derivatives and benzyl ketals [for example, Ciba Specialty Chemicals, trade name: Irgacure 651], ⁇ -hydroxyacetophenones, as intramolecular cleavage types.
  • Ciba Specialty Chemicals, Inc. trade names: Darocur 1173, Irgacure 184, Irgacure 127], ⁇ -aminoacetophenones [for example, Ciba Specialty Chemicals, Inc., trade names: Irgacure 907, Irgacure 369], a combination of ⁇ -aminoacetophenones and thioxanthones (for example, isopropylthioxanthone, diethylthioxanthone), acylphosphine oxides [for example, manufactured by Ciba Specialty Chemicals Co., Ltd.
  • oligomerized ⁇ -hydroxyacetophenone and acrylated benzophenones are preferable. More specifically, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] [for example, Lamberti S., et al. p.
  • the blending amount of the photopolymerization initiator is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass in total of the styrene-butadiene copolymer (A) and the polythiol (B), and 0.05 to The range of 15 parts by mass is further preferable, and the range of 0.1 to 10 parts by mass is even more preferable.
  • thermosetting the thiol-containing liquid rubber composition of the present invention a radical generator that generates radicals by heat and initiates (accelerates) thermosetting of the composition may be blended.
  • a thermal radical generator organic peroxides and azobis compounds are preferred. These thermal radical generators may be used individually by 1 type, and may be used in combination of 2 or more type.
  • organic peroxide examples include 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-amylperoxy-2-ethylhexanoate, di (2-t -Butylperoxyisopropyl) benzene, benzoyl peroxide, 1,1'-di (t-butylperoxy) cyclohexane, di (3,5,5-trimethylhexanoyl) peroxide, t-butylperoxyneodecano And t-hexylperoxyneodecanoate, dicumyl peroxide and the like.
  • azobis compounds examples include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2,2'-azobis (2 -Methyl propionate) and the like.
  • the amount of the radical generator is not particularly limited, but is preferably in the range of 0.05 to 30 parts by mass with respect to 100 parts by mass of the styrene-butadiene copolymer (A), and 0.2. The range of ⁇ 20 parts by mass is further preferred, and the range of 0.5 to 15 parts by mass is even more preferred. If the amount of the radical generator is 0.05 parts by mass or more, the thermosetting reaction of the composition can be started, and if it is 30 parts by mass or less, gas generation due to the radical generator, residual radicals Bleeding out and outgas generation of the generating agent can be suppressed.
  • thiol-containing liquid rubber composition of the present invention is excellent in both photocurability and thermosetting properties, various applications, in particular, rollers such as developing rollers, charging rollers, and transfer rollers used in printers and copiers, etc. It is useful in blades such as developing blades and cleaning blades, gasket members, display sealing materials, architectural sealing materials, and the like.
  • Styrene-butadiene copolymer is also referred to as “SB copolymer”.
  • Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
  • the liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer A) having a terminal styrene content of 35% by mass and a vinyl bond content of the butadiene portion of 65%. Met. Further, the number average molecular weight was 5,200, the weight average molecular weight was 6,700, and the molecular weight distribution was 1.28.
  • Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
  • the liquid rubber obtained as described above is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer B) having a terminal styrene content of 55% by mass and a vinyl bond content of the butadiene portion of 65%.
  • SB copolymer B hydroxyl-terminated styrene-butadiene copolymer having a terminal styrene content of 55% by mass and a vinyl bond content of the butadiene portion of 65%.
  • the number average molecular weight was 4000, the weight average molecular weight was 4800, and the molecular weight distribution was 1.20.
  • Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
  • the liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer C) with a terminal styrene content of 23% by mass and a vinyl bond content of the butadiene portion of 65%.
  • SB copolymer C hydroxyl-terminated styrene-butadiene copolymer
  • Met The number average molecular weight was 4,900, the weight average molecular weight was 6,200, and the molecular weight distribution was 1.26.
  • Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
  • the liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer D) with a terminal styrene content of 35% by mass and a vinyl bond content of the butadiene portion of 78%. Met.
  • the number average molecular weight was 4,400, the weight average molecular weight was 5,300, and the molecular weight distribution was 1.20.
  • Polymerization is carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 108.0 ml of a 1 mol / liter ethylene oxide cyclohexane solution is added, and further stirred for 2 hours, and then 50 ml of isopropyl alcohol is added. did. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
  • the photocurable liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer E) having a terminal styrene content of 29% by mass and a vinyl bond content in the butadiene portion.
  • SB copolymer E hydroxyl-terminated styrene-butadiene copolymer having a terminal styrene content of 29% by mass and a vinyl bond content in the butadiene portion.
  • the number average molecular weight was 12,500, the weight average molecular weight was 16,000, and the molecular weight distribution was 1.26.
  • Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., then 70 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and after further stirring for 2 hours, 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
  • the photocurable liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer F) having a terminal styrene content of 35% by mass, and a vinyl bond content in the butadiene portion.
  • SB copolymer F hydroxyl-terminated styrene-butadiene copolymer having a terminal styrene content of 35% by mass, and a vinyl bond content in the butadiene portion.
  • the number average molecular weight was 17,200, the weight average molecular weight was 21,500, and the molecular weight distribution was 1.25.
  • Irgacure 184D manufactured by Ciba Specialty Chemicals, 1-hydroxycyclohexyl phenyl ketone
  • Irgacure 184D is blended in an amount of 1 part by mass with respect to 100 parts by mass of liquid rubber, irradiated with 7000 mJ / cm 2 of ultraviolet rays, and then cured at 23 ° C. Sex was assessed by palpation. The case where it was hardened completely as a solid as compared with the solution was indicated as ⁇ , the case where it was slightly cured as ⁇ , and the case where it was not cured at all as ⁇ . The results are shown in Tables 1-5.
  • Trigonox 121 manufactured by Akzo, t-amylperoxy-2-ethylhexanoate was blended in an amount of 5 parts by mass with respect to 100 parts by mass of the liquid rubber and cured at 150 ° C. for 10 minutes. The curability of the composition at this time was evaluated by palpation. The case where it was completely cured as compared with the solution was evaluated as ⁇ , the case where it was slightly cured as ⁇ , and the case where it did not at all as ⁇ . The results are shown in Tables 1-5.
  • SB copolymer B synthesized by the above method

Abstract

Disclosed is a rubber composition comprising a styrene-butadiene copolymer and having improved compatibility with a thiol crosslinking agent and also having increased curability. Specifically disclosed is a thiol-containing liquid rubber composition, comprising (A) a styrene-butadiene copolymer which is liquid at 25˚C and (B) a polythiol derived from mercaptocarboxylic acid, wherein the styrene-butadiene copolymer (A) preferably has a bound styrene content of 20 to 90% by mass.

Description

チオール含有液状ゴム組成物Thiol-containing liquid rubber composition
　本発明は、液状であるスチレン－ブタジエン共重合体と特定のポリチオールを配合した硬化性に優れるチオール含有液状ゴム組成物に関する。 The present invention relates to a thiol-containing liquid rubber composition excellent in curability in which a liquid styrene-butadiene copolymer and a specific polythiol are blended.
　昨今、プリンターや複写機等に用いられる現像ローラ、帯電ローラ、転写ローラ等のローラ類、現像ブレード、クリーニングブレード等のブレード類、ガスケット部材、ディスプレイ用封止材、建築用シーリング材等の様々な用途において、スチレン－ブタジエン共重合体のようなゴム系樹脂を用いたゴム組成物が採用されている。かかるゴム系樹脂を硬化させる際には、トリアジンチオール化合物のようなチオール系架橋剤などを添加することにより、硬化処理が施される（特許文献１参照）。 Various types of rollers such as developing rollers, charging rollers, and transfer rollers used in printers and copiers, blades such as developing blades and cleaning blades, gasket members, display sealing materials, and architectural sealing materials. In use, a rubber composition using a rubber-based resin such as a styrene-butadiene copolymer is employed. When curing such a rubber-based resin, a curing treatment is performed by adding a thiol-based crosslinking agent such as a triazine thiol compound (see Patent Document 1).
特開２０００－１７７２３４号公報JP 2000-177234 A
　しかしながら、こうしたチオール系架橋剤は極性を有するために、スチレン－ブタジエン共重合体のようなゴム系樹脂への相溶性が良好ではなく、溶液の均一性不良により光硬化或いは熱硬化させた際に未硬化の部分が生じたり、相分離などが発生して貯蔵安定性が悪くなったりするおそれがある。こうした現象は組成物の不透明化を進行させるおそれもあるため、特に、光硬化の場合には、光の透過性が悪化して内部の硬化が不充分となるおそれもある。 However, since these thiol-based crosslinking agents have polarity, they are not compatible with rubber-based resins such as styrene-butadiene copolymers, and when photocured or thermally cured due to poor solution uniformity. There is a possibility that an uncured portion may be formed or phase separation may occur, resulting in poor storage stability. Since such a phenomenon may cause the composition to become opaque, in particular, in the case of photocuring, there is a possibility that the light transmittance is deteriorated and the internal curing becomes insufficient.
　そこで、本発明は、かかるスチレン－ブタジエン共重合体を採用しつつ、チオール系架橋剤との相溶性を改善し、硬化性を向上させたゴム組成物を提供することを目的としている。 Accordingly, an object of the present invention is to provide a rubber composition having improved curability by improving compatibility with a thiol-based crosslinking agent while employing such a styrene-butadiene copolymer.
　本発明者は、上記課題を解決すべく、特定のスチレン－ブタジエン共重合体とポリチオールとを配合したチオール含有液状ゴム組成物を見出し、本発明を完成させるに至った。
　すなわち、本発明のチオール含有液状ゴム組成物は、
　２５℃において液状であるスチレン－ブタジエン共重合体（Ａ）と、
　メルカプトカルボン酸由来のポリチオール（Ｂ）と
を含むことを特徴とする。
　また、前記スチレン－ブタジエン共重合体（Ａ）の結合スチレン含有量は、２０～９０質量％であるのが好ましく、ランダム共重合体であるのが望ましい。 In order to solve the above problems, the present inventors have found a thiol-containing liquid rubber composition containing a specific styrene-butadiene copolymer and polythiol, and have completed the present invention.
That is, the thiol-containing liquid rubber composition of the present invention is
A styrene-butadiene copolymer (A) which is liquid at 25 ° C .;
And a polythiol (B) derived from mercaptocarboxylic acid.
The styrene-butadiene copolymer (A) preferably has a bound styrene content of 20 to 90% by mass, and is preferably a random copolymer.
　前記ポリチオール（Ｂ）は、テトラエチレングリコールビス(３-メルカプトプロピオネート)、トリメチロールプロパントリス(３-メルカプトプロピオネート)、トリス[(３-メルカプトプロピオニロキシ)-エチル]イソシアヌレート、ペンタエリスリトールテトラキス(３-メルカプトプロピオネート)、ジペンタエリスリトールヘキサキス(３-メルカプトプロピオネート)、１，４-ビス(３-メルカプトブチリルオキシ)ブタン、ペンタエリスリトールテトラキス(３-メルカプトブチレート)、及び１，３，５-トリス(３-メルカプトブチルオキシエチル)-１，３，５-トリアジン-２，４，６(１Ｈ，３Ｈ，５Ｈ)-トリオンからなる群から選択される少なくとも一種であるのが好ましい。 The polythiol (B) includes tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, penta Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) And at least one selected from the group consisting of 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Preferably there is.
　前記ポリチオール（Ｂ）の含有量は、スチレン－ブタジエン共重合体（Ａ）１００重量部に対して、４０質量部以下であってもよい。
　前記スチレン－ブタジエン共重合体（Ａ）の数平均分子量（Ｍｎ）は、１２００～４００００であるのが望ましい。 The content of the polythiol (B) may be 40 parts by mass or less with respect to 100 parts by weight of the styrene-butadiene copolymer (A).
The number average molecular weight (Mn) of the styrene-butadiene copolymer (A) is preferably 1200 to 40000.
　本発明のチオール含有液状ゴム組成物によれば、ゴム系樹脂であるスチレン－ブタジエン共重合体と、架橋剤としてのポリチオール（Ｂ）との相溶性に非常に優れており、溶液の不均一による未硬化部分の発生を回避することができる。また、未硬化部分の発生を有効に低減することができるため、光硬化性・熱硬化性のいずれであっても良好な硬化性を発揮することができる。 According to the thiol-containing liquid rubber composition of the present invention, the compatibility between the styrene-butadiene copolymer as a rubber resin and the polythiol (B) as a crosslinking agent is extremely excellent, and due to the nonuniformity of the solution. Generation | occurrence | production of an unhardened part can be avoided. Moreover, since generation | occurrence | production of an unhardened part can be reduced effectively, even if it is any of photocurability and thermosetting, favorable sclerosis | hardenability can be exhibited.
　したがって、均一で安定した性能を有する組成物を得ることが可能となり、プリンターや複写機等に用いられる現像ローラ、帯電ローラ、転写ローラ等のローラ類、現像ブレード、クリーニングブレード等のブレード類、ガスケット部材、ディスプレイ用封止材、建築用シーリング材等の広範な用途において有用である。 Therefore, it becomes possible to obtain a composition having uniform and stable performance, and rollers such as developing rollers, charging rollers, and transfer rollers used in printers and copying machines, blades such as developing blades and cleaning blades, and gaskets. It is useful in a wide range of applications such as members, sealing materials for displays, and sealing materials for buildings.
　以下、本発明について詳細に説明する。
　本発明のチオール含有液状ゴム組成物は、
　２５℃において液状であるスチレン－ブタジエン共重合体（Ａ）と、
　メルカプトカルボン酸由来のポリチオール（Ｂ）と
を含むことを特徴とし、必要に応じて光硬化或いは熱硬化させる際に用いる開始剤等を添加することができる。 Hereinafter, the present invention will be described in detail.
The thiol-containing liquid rubber composition of the present invention is
A styrene-butadiene copolymer (A) which is liquid at 25 ° C .;
It contains polythiol (B) derived from mercaptocarboxylic acid, and an initiator or the like used for photocuring or thermosetting can be added as necessary.
　[スチレン－ブタジエン共重合体（Ａ）]
　本発明のチオール含有液状ゴム組成物に用いるスチレン－ブタジエン共重合体（Ａ）は、２５℃（室温）において液状である。一般に、ブタジエンゴムやイソプレンゴムなどのジエン系ゴムは非極性であるため、チオール系架橋剤のような極性を有する化合物との相溶性が芳しくない。しかしながら、本発明のように、このような液状のスチレン－ブタジエン共重合体（Ａ）を採用しつつ、後述する特定のチオール系架橋剤を用いると、スチレン－ブタジエン共重合体も同様に非極性であるにも関わらず相溶性が良好となり、これら各成分の混合作業が容易となる。 [Styrene-butadiene copolymer (A)]
The styrene-butadiene copolymer (A) used in the thiol-containing liquid rubber composition of the present invention is liquid at 25 ° C. (room temperature). In general, diene rubbers such as butadiene rubber and isoprene rubber are non-polar, and thus have poor compatibility with polar compounds such as thiol cross-linking agents. However, as in the present invention, when such a liquid styrene-butadiene copolymer (A) is employed and a specific thiol-based cross-linking agent described later is used, the styrene-butadiene copolymer is similarly nonpolar. In spite of this, the compatibility becomes good and the mixing operation of these components becomes easy.
　上記スチレン－ブタジエン共重合体（Ａ）の製造方法は、特に限定されず、１，３-ブタジエンであるモノマーと、スチレンモノマーとを共重合体して得ることができる。ここで、共重合には、リチウム系の重合開始剤を使用することができ、さらに必要に応じてランダマイザー等を使用してもよい。また、リチウム系の重合開始剤を用いてアニオン重合で製造する際には、さらに、任意に各種変性剤でポリマー鎖のリビング末端を変性することも可能である。例えば、変性剤としてエチレンオキサイドやプロピレンオキサイド等のアルキレンオキサイドを使用することで、両末端又は片末端に水酸基を有するジエン系ポリマーを得ることができる。 The method for producing the styrene-butadiene copolymer (A) is not particularly limited, and can be obtained by copolymerizing a monomer that is 1,3-butadiene and a styrene monomer. Here, a lithium-based polymerization initiator can be used for the copolymerization, and a randomizer or the like may be used as necessary. In addition, when anionic polymerization is performed using a lithium-based polymerization initiator, it is also possible to optionally modify the living terminal of the polymer chain with various modifiers. For example, by using an alkylene oxide such as ethylene oxide or propylene oxide as a modifier, a diene polymer having hydroxyl groups at both ends or one end can be obtained.
　なお、上記スチレン－ブタジエン共重合体（Ａ）における共重合体中の単量体の配列は、特に限定されず、ランダム共重合体、交互共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよいが、ランダム共重合体であるのが好ましい。ランダム共重合体であると、不飽和基が共重合体中によりランダムに配置されることとなり、ポリチオール（Ｂ）との相溶性向上、さらには硬化物の耐熱性向上などに寄与することができる。ランダム共重合体を得るには、例えば、テトラヒドロフラン等のエーテルや２，２-ビス(テトラヒドロフリル)プロパンのようなランダマイザーを添加して、重合を行うとよい。 In addition, the arrangement of the monomers in the copolymer in the styrene-butadiene copolymer (A) is not particularly limited, and is a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. Any of them may be used, but a random copolymer is preferable. If it is a random copolymer, unsaturated groups will be arranged more randomly in the copolymer, which can contribute to improved compatibility with polythiol (B) and further to improved heat resistance of the cured product. . In order to obtain a random copolymer, for example, an ether such as tetrahydrofuran or a randomizer such as 2,2-bis (tetrahydrofuryl) propane may be added for polymerization.
　上記スチレン－ブタジエン共重合体（Ａ）は、数平均分子量（Ｍｎ）が１２００～４００００、好ましくは３０００～３００００であるのが望ましい。数平均分子量（Ｍｎ）が１２００以上であると、含有不飽和基の量も問題なく、強伸度等の物性も良好であり、また、４００００以下であると、ポリチオールとの相溶性、或いは粘度の問題から成型時の加工性も良好である。 The styrene-butadiene copolymer (A) has a number average molecular weight (Mn) of 1200 to 40000, preferably 3000 to 30000. When the number average molecular weight (Mn) is 1200 or more, there is no problem in the amount of the unsaturated group contained, the physical properties such as the strength and elongation are good, and when it is 40000 or less, the compatibility with the polythiol, or the viscosity Due to this problem, the processability at the time of molding is also good.
　上記スチレン－ブタジエン共重合体（Ａ）としては、結合スチレン含量が９０質量％以下、好ましくは２５～６５質量％であるのが望ましい。また、ブタジエン部分のビニル結合含量は２０～８５％、好ましくは２５～８０％であるのが望ましい。かかる範囲の結合スチレン含量、またはブタジエン部分のビニル結合含量を有する液状スチレン－ブタジエン共重合体を使用することで、硬化性、ポリチオールとの相溶性がより良好となる。これは、スチレン部分が相溶性に寄与し、ビニル結合部分が特に硬化性に寄与するためであると考えられる。 The styrene-butadiene copolymer (A) has a bound styrene content of 90% by mass or less, preferably 25 to 65% by mass. The vinyl bond content of the butadiene moiety is 20 to 85%, preferably 25 to 80%. By using a liquid styrene-butadiene copolymer having such a bound styrene content or a vinyl bond content of the butadiene portion, the curability and the compatibility with the polythiol become better. This is presumably because the styrene portion contributes to compatibility and the vinyl bond portion particularly contributes to curability.
　また、上記スチレン－ブタジエン共重合体（Ａ）は、両末端又は片末端に水酸基を有するのが望ましい。かかるスチレン－ブタジエン共重合体（Ａ）を使用することで、ポリチオールとの相溶性がさらに向上することとなる。 The styrene-butadiene copolymer (A) preferably has hydroxyl groups at both ends or one end. By using such a styrene-butadiene copolymer (A), the compatibility with polythiol is further improved.
　[メルカプトカルボン酸由来のポリチオール（Ｂ）]
　本発明のチオール含有液状ゴム組成物に用いるポリチオール（Ｂ）は、メルカプトカルボン酸由来のポリチオールであり、好ましくは３-メルカプトプロピオン酸由来のポリチオールである。該ポリチオール（Ｂ）は、好ましくは分子中にメルカプトアシロキシ基を複数有し、より好ましくは２～６個有する。ここで、メルカプトアシロキシ基として、具体的には、３-メルカプトプロピオニロキシ基［ＨＳ－(ＣＨ2)2－ＣＯＯ－］、３-メルカプトブチルオキシ基［ＨＳ－ＣＨ(ＣＨ3)－ＣＨ2－ＣＯＯ－］等が挙げられ、３-メルカプトプロピオニロキシ基が好ましい。該メルカプトカルボン酸由来のポリチオール（Ｂ）は、例えば熱ラジカル発生剤などを配合した場合、該熱ラジカル発生剤由来のラジカルによってチイルラジカルを発生し、該チイルラジカルがスチレン－ブタジエン共重合体（Ａ）の不飽和結合に付加して、硬化（架橋）反応を促進することとなる。 [Mercaptocarboxylic acid-derived polythiol (B)]
The polythiol (B) used in the thiol-containing liquid rubber composition of the present invention is a polythiol derived from mercaptocarboxylic acid, and preferably a polythiol derived from 3-mercaptopropionic acid. The polythiol (B) preferably has a plurality of mercaptoacyloxy groups in the molecule, more preferably 2-6. Here, as the mercaptoacyloxy group, specifically, 3-mercaptopropionyloxy group [HS— (CH 2 ) 2 —COO—], 3-mercaptobutyloxy group [HS—CH (CH 3 ) —CH 2- COO-] and the like, and a 3-mercaptopropionyloxy group is preferable. When the mercaptocarboxylic acid-derived polythiol (B) is blended with, for example, a thermal radical generator, a thiyl radical is generated by the radical derived from the thermal radical generator, and the thiyl radical is converted into the styrene-butadiene copolymer (A). Adding to the unsaturated bond promotes the curing (crosslinking) reaction.
　上記ポリチオール（Ｂ）として、具体的には、下記化学式(I)で表わされるテトラエチレングリコールビス(３-メルカプトプロピオネート)、下記化学式(II)で表わされるトリメチロールプロパントリス(３-メルカプトプロピオネート)、下記化学式(III)で表わされるトリス[(３-メルカプトプロピオニロキシ)-エチル]イソシアヌレート、下記化学式(IV)で表わされるペンタエリスリトールテトラキス(３-メルカプトプロピオネート)、下記化学式(V)で表わされるジペンタエリスリトールヘキサキス(３-メルカプトプロピオネート)、下記化学式(VI)で表わされる１，４-ビス(３-メルカプトブチリルオキシ)ブタン、下記化学式(VII)で表わされるペンタエリスリトールテトラキス(３-メルカプトブチレート)、及び下記化学式(VIII)で表わされる１，３，５-トリス(３-メルカプトブチルオキシエチル) -１，３，５-トリアジン-２，４，６(１Ｈ，３Ｈ，５Ｈ)-トリオンが好ましい。 Specific examples of the polythiol (B) include tetraethylene glycol bis (3-mercaptopropionate) represented by the following chemical formula (I) and trimethylolpropane tris (3-mercaptoprote represented by the following chemical formula (II). Pionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate represented by the following chemical formula (III), pentaerythritol tetrakis (3-mercaptopropionate) represented by the following chemical formula (IV), Dipentaerythritol hexakis (3-mercaptopropionate) represented by (V), 1,4-bis (3-mercaptobutyryloxy) butane represented by the following chemical formula (VI), represented by the following chemical formula (VII) Pentaerythritol tetrakis (3-mercaptobutyrate) and 1,3,5-tris represented by the following chemical formula (VIII) ( 3-Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000002
　上記ポリチオール（Ｂ）は、スチレン－ブタジエン共重合体（Ａ）との相溶性が高く、均一で性能の安定した組成物を得ることができる。なお、これらポリチオール（Ｂ）は、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 The polythiol (B) has a high compatibility with the styrene-butadiene copolymer (A), and a uniform and stable composition can be obtained. In addition, these polythiol (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
　上記ポリチオール（Ｂ）の配合量は、特に限定されるものではないが、上記スチレン－ブタジエン共重合体（Ａ）１００質量部に対して、４０質量部以下の範囲が好ましく、３～３５質量部の範囲が更に好ましく、５～３０質量部の範囲がより一層好ましい。ポリチオール（Ｂ）の配合量が４０質量部以下であれば、液状ゴムとの良好な相溶性を維持でき、さらに３質量部以上であれば、組成物の光または熱硬化性を充分に向上させることができるので望ましい。 The blending amount of the polythiol (B) is not particularly limited, but is preferably in the range of 40 parts by mass or less with respect to 100 parts by mass of the styrene-butadiene copolymer (A), and 3 to 35 parts by mass. The range of 5 to 30 parts by mass is even more preferable. If the blending amount of the polythiol (B) is 40 parts by mass or less, good compatibility with the liquid rubber can be maintained, and if it is 3 parts by mass or more, the light or thermosetting property of the composition is sufficiently improved. This is desirable.
　[チオール含有液状ゴム組成物]
　本発明のチオール含有液状ゴム組成物には、上記成分のほか、本発明の目的を阻害しない範囲内であれば、上記スチレン－ブタジエン共重合体（Ａ）以外の、いわゆるジエン系ポリマーを含有させてもよい。 [Thiol-containing liquid rubber composition]
In addition to the above components, the thiol-containing liquid rubber composition of the present invention contains a so-called diene polymer other than the above styrene-butadiene copolymer (A) as long as it does not impair the object of the present invention. May be.
　上記ジエン系ポリマーとしては、例えば、天然ゴム、ポリイソプレン、ポリブタジエン、ブタジエン－イソプレン共重合体、イソブチレン－イソプレン共重合体、ブタジエン－アクリロニトリル共重合体、スチレン－イソプレン共重合体、ポリクロロプレン等が挙げられる。これらジエン系ポリマーの末端は、変性されていてもよいし、変性されていなくてもよい。 Examples of the diene polymer include natural rubber, polyisoprene, polybutadiene, butadiene-isoprene copolymer, isobutylene-isoprene copolymer, butadiene-acrylonitrile copolymer, styrene-isoprene copolymer, and polychloroprene. It is done. The terminal of these diene polymers may be modified or may not be modified.
　また、本発明のチオール含有液状ゴム組成物を光硬化させる際には、光重合開始剤を配合してもよい。光重合開始剤としては、具体的には、分子内開裂型として、ベンゾイン誘導体類、ベンジルケタール類［例えば、チバ・スペシャルティ・ケミカルズ（株）製、商品名：イルガキュア６５１］、α－ヒドロキシアセトフェノン類［例えば、チバ・スペシャルティ・ケミカルズ（株）製、商品名：ダロキュア１１７３、イルガキュア１８４、イルガキュア１２７］、α－アミノアセトフェノン類［例えば、チバ・スペシャルティ・ケミカルズ（株）製、商品名：イルガキュア９０７、イルガキュア３６９］、α－アミノアセトフェノン類とチオキサントン類（例えば、イソプロピルチオキサントン、ジエチルチオキサントン）との併用、アシルホスフィンオキサイド類［例えば、チバ・スペシャルティ・ケミカルズ（株）製、商品名：イルガキュア８１９］等が挙げられ、水素引き抜き型として、ベンゾフェノン類とアミンの併用、チオキサントンとアミンの併用等が挙げられる。また、分子内開裂型と水素引き抜き型を併用してもよい。中でもオリゴマー化したα－ヒドロキシアセトフェノン及びアクリレート化したベンゾフェノン類が好ましい。より具体的には、オリゴ［２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン］［例えば、Ｌａｍｂｅｒｔｉ Ｓ．ｐ．Ａ製、商品名：ＥＳＡＣＵＲＥ ＫＩＰ１５０等］、アクリル化ベンゾフェノン［例えば、ダイセル・ユー・シー・ビー（株）製、商品名：Ｅｂｅｃｒｙｌ Ｐ１３６等］、イミドアクリレート等が挙げられる。 Further, when the thiol-containing liquid rubber composition of the present invention is photocured, a photopolymerization initiator may be blended. Specific examples of photopolymerization initiators include benzoin derivatives and benzyl ketals [for example, Ciba Specialty Chemicals, trade name: Irgacure 651], α-hydroxyacetophenones, as intramolecular cleavage types. [For example, Ciba Specialty Chemicals, Inc., trade names: Darocur 1173, Irgacure 184, Irgacure 127], α-aminoacetophenones [for example, Ciba Specialty Chemicals, Inc., trade names: Irgacure 907, Irgacure 369], a combination of α-aminoacetophenones and thioxanthones (for example, isopropylthioxanthone, diethylthioxanthone), acylphosphine oxides [for example, manufactured by Ciba Specialty Chemicals Co., Ltd. 819], and the like, as a hydrogen abstraction type, combined use of benzophenones and amines, combination and the like of the thioxanthone and amine. Further, an intramolecular cleavage type and a hydrogen abstraction type may be used in combination. Among them, oligomerized α-hydroxyacetophenone and acrylated benzophenones are preferable. More specifically, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] [for example, Lamberti S., et al. p. A product, trade name: ESACURE KIP150, etc.], acrylated benzophenone [for example, Daicel UCB Co., Ltd., trade name: Ebecryl セ ル P136, etc.], imide acrylate, and the like.
　また、光重合開始剤として、上述のもの以外に、１－［４－（２－ヒドロキシエトキシ）フェニル］－２－メチル－１－プロパン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニルケトン［例えば、Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ（株）製、商品名：ＩＲＡＧＡＣＵＲＥ１８４等］、１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２，４，６－トリメチルベンゾイルフェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルフェニルフェニルエトキシホスフィンオキサイド、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、２－メチル－１－［（４－メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、ベンゾイルメチルエーテル、ベンゾイルエチルエーテル、ベンゾイルブチルエーテル、ベンゾイルイソプロピルエーテル、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド、２－ヒドロキシ－２－メチル－［４－（１－メチルビニル）フェニル］プロパノールオリゴマー、２－ヒドロキシ－２－メチル－［４－（１－メチルビニル）フェニル］プロパノールオリゴマーと２－ヒドロキシ－２－メチル－１－フェニル－１－プロパノンの混合物、イソプロピルチオキサントン、ｏ－ベンゾイル安息香酸メチル及び［４－（メチルフェニルチオ）フェニル］フェニルメタン等も用いることができる。 In addition to the above-mentioned photopolymerization initiators, 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone [for example, , Ciba Specialty Chemicals Co., Ltd., trade name: IRAGACURE 184, etc.], 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone mixture, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4 , 6-trimethylbenzoylphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2 -Methyl-1-fe Nyl-propan-1-one, 2-methyl-1-[(4-methylthio) phenyl] -2-morpholinopropan-1-one, benzoyl methyl ether, benzoyl ethyl ether, benzoyl butyl ether, benzoyl isopropyl ether, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, 2-hydroxy-2-methyl- [4- (1-methyl) Vinyl) phenyl] propanol oligomer and a mixture of 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthone, methyl o-benzoylbenzoate and [4- (methylphenylthio) phenyl] phenylmethane are also used. be able to
　上記光重合開始剤の配合量は、スチレン－ブタジエン共重合体（Ａ）とポリチオール（Ｂ）との合計１００質量部に対して、０．０１～２０質量部の範囲が好ましく、０．０５～１５質量部の範囲が更に好ましく、０．１～１０質量部の範囲がより一層好ましい。 The blending amount of the photopolymerization initiator is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass in total of the styrene-butadiene copolymer (A) and the polythiol (B), and 0.05 to The range of 15 parts by mass is further preferable, and the range of 0.1 to 10 parts by mass is even more preferable.
　さらに、本発明のチオール含有液状ゴム組成物を熱硬化させる際には、熱によりラジカルを発生して、組成物の熱硬化を開始させる（促進する）作用を担うラジカル発生剤を配合してもよい。かかる熱ラジカル発生剤としては、有機過酸化物及びアゾビス系化合物が好ましい。これら熱ラジカル発生剤は、一種単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 Furthermore, when thermosetting the thiol-containing liquid rubber composition of the present invention, a radical generator that generates radicals by heat and initiates (accelerates) thermosetting of the composition may be blended. Good. As such a thermal radical generator, organic peroxides and azobis compounds are preferred. These thermal radical generators may be used individually by 1 type, and may be used in combination of 2 or more type.
　上記有機過酸化物としては、例えば、１，１-ジ(ｔ-ヘキシルパーオキシ)-３，３，５-トリメチルシクロヘキサン、ｔ-アミルパーオキシ-２-エチルヘキサノエート、ジ(２-ｔ-ブチルパーオキシイソプロピル)ベンゼン、過酸化ベンゾイル、１，１’-ジ(ｔ-ブチルパーオキシ)シクロヘキサン、ジ(３，５，５-トリメチルヘキサノイル)パーオキサイド、ｔ-ブチルパーオキシネオデカノエート、ｔ-ヘキシルパーオキシネオデカノエート、ジクミルパーオキサイド等が挙げられる。 Examples of the organic peroxide include 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-amylperoxy-2-ethylhexanoate, di (2-t -Butylperoxyisopropyl) benzene, benzoyl peroxide, 1,1'-di (t-butylperoxy) cyclohexane, di (3,5,5-trimethylhexanoyl) peroxide, t-butylperoxyneodecano And t-hexylperoxyneodecanoate, dicumyl peroxide and the like.
　上記アゾビス系化合物としては、例えば、２，２’-アゾビス(２-メチルプロピオニトリル)、２，２’-アゾビス(２-メチルブチロニトリル)、２，２’-アゾビス(２，４-ジメチルバレロニトリル)、２，２’-アゾビス(４-メトキシ-２，４-ジメチルバレロニトリル)、２-フェニルアゾ-４-メトキシ-２，４-ジメチルバレロニトリル、ジメチル２，２’-アゾビス(２-メチルプロピオネート)等が挙げられる。 Examples of the azobis compounds include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2,2'-azobis (2 -Methyl propionate) and the like.
　上記ラジカル発生剤の配合量は、特に限定されるものではないが、上記スチレン－ブタジエン共重合体（Ａ）１００質量部に対して、０.０５～３０質量部の範囲が好ましく、０.２～２０質量部の範囲が更に好ましく、０.５～１５質量部の範囲がより一層好ましい。ラジカル発生剤の配合量が０.０５質量部以上であれば、組成物の熱硬化反応を開始させることができ、また、３０質量部以下であれば、ラジカル発生剤起因のガス発生、残留ラジカル発生剤のブリードアウト、アウトガス発生を抑制できる。 The amount of the radical generator is not particularly limited, but is preferably in the range of 0.05 to 30 parts by mass with respect to 100 parts by mass of the styrene-butadiene copolymer (A), and 0.2. The range of ˜20 parts by mass is further preferred, and the range of 0.5 to 15 parts by mass is even more preferred. If the amount of the radical generator is 0.05 parts by mass or more, the thermosetting reaction of the composition can be started, and if it is 30 parts by mass or less, gas generation due to the radical generator, residual radicals Bleeding out and outgas generation of the generating agent can be suppressed.
　上述した本発明のチオール含有液状ゴム組成物は、光硬化性および熱硬化性共に優れるため、種々の用途、特に、プリンターや複写機等に用いられる現像ローラ、帯電ローラ、転写ローラ等のローラ類、現像ブレード、クリーニングブレード等のブレード類、ガスケット部材、ディスプレイ用封止材、建築用シーリング材等において有用である。 Since the above-described thiol-containing liquid rubber composition of the present invention is excellent in both photocurability and thermosetting properties, various applications, in particular, rollers such as developing rollers, charging rollers, and transfer rollers used in printers and copiers, etc. It is useful in blades such as developing blades and cleaning blades, gasket members, display sealing materials, architectural sealing materials, and the like.
　以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、「スチレン－ブタジエン共重合体」を「ＳＢ共重合体」ともいう。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Styrene-butadiene copolymer” is also referred to as “SB copolymer”.
　[製造例１：ＳＢ共重合体Ａの合成]
　充分に脱水精製したシクロヘキサン溶媒中に、１，３-(ジイソプロペニル)ベンゼン １モルを添加した後、トリエチルアミン ２モル、ｓｅｃ-ブチルリチウム ２モルを順次添加し、５０℃で２時間撹拌して、ジリチウム系重合開始剤を調製した。 [Production Example 1: Synthesis of SB copolymer A]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a cyclohexane solvent that has been thoroughly dehydrated and purified, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added, followed by stirring at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared.
　アルゴン置換した７リットルの重合リアクターに、脱水精製したシクロヘキサンを１.５ｋｇ、２２.９質量％の１，３-ブタジエンモノマーのヘキサン溶液を１.６５ｋｇ、２０.０質量％のスチレンモノマーのシクロヘキサン溶液を１.００ｋｇ、１.１５モル／リットルの２，２-ビス(テトラヒドロフリル)プロパンのヘキサン溶液を２００ｍｌ添加した後、０.５モル／リットルの上記ジリチウム系重合開始剤を２３０ｍｌ添加して重合を開始させた。 In a 7 liter polymerization reactor purged with argon, 1.5 kg of dehydrated and purified cyclohexane, 1.65 kg of a hexane solution of 22.9% by mass of 1,3-butadiene monomer, and a cyclohexane solution of 20.0% by mass of styrene monomer 200 ml of a hexane solution of 1.00 kg of 1.15 mol / liter of 2,2-bis (tetrahydrofuryl) propane was added, and then 230 ml of the above dilithium polymerization initiator of 0.5 mol / liter was added for polymerization. Was started.
　重合リアクターを５０℃に昇温しながら、１.５時間重合を行った後、１モル／リットルのエチレンオキシドのシクロヘキサン溶液を２５４ｍｌ添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、充分に乾燥させて、両末端が水酸基である２５℃において液状の液状ゴムを得た。 Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
　以上のようにして得られた液状ゴムは両末端ヒドロキシル基スチレン－ブタジエン共重合体（ＳＢ共重合体Ａ）であり、結合スチレン含量が３５質量％であり、ブタジエン部分のビニル結合含量が６５％であった。また、数平均分子量が５２００、重量平均分子量が６７００、分子量分布が１.２８であった。 The liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer A) having a terminal styrene content of 35% by mass and a vinyl bond content of the butadiene portion of 65%. Met. Further, the number average molecular weight was 5,200, the weight average molecular weight was 6,700, and the molecular weight distribution was 1.28.
　[製造例２：ＳＢ共重合体Ｂの合成例]
　充分に脱水精製したシクロヘキサン溶媒中に、１，３-(ジイソプロペニル)ベンゼン １モルを添加した後、トリエチルアミン ２モル、ｓｅｃ-ブチルリチウム ２モルを順次添加し、５０℃で２時間撹拌して、ジリチウム系重合開始剤を調製した。 [Production Example 2: Synthesis Example of SB Copolymer B]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a cyclohexane solvent that has been thoroughly dehydrated and purified, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added, followed by stirring at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared.
　アルゴン置換した７リットルの重合リアクターに、脱水精製したシクロヘキサンを１.４５ｋｇ、２２.９質量％の１，３-ブタジエンモノマーのヘキサン溶液を１.１５ｋｇ、２０.０質量％のスチレンモノマーのシクロヘキサン溶液を１.６５ｋｇ、１.１５モル／リットルの２，２-ビス(テトラヒドロフリル)プロパンのヘキサン溶液を２００ｍｌ添加した後、０.５モル／リットルの上記ジリチウム系重合開始剤を２３０ｍｌ添加して重合を開始させた。 In a 7 liter polymerization reactor purged with argon, 1.45 kg of dehydrated and purified cyclohexane, 1.15 kg of hexane solution of 22.9% by mass of 1,3-butadiene monomer, and 20.0% by mass of cyclohexane solution of styrene monomer. 1.65 kg of 1.15 mol / liter 2,2-bis (tetrahydrofuryl) propane hexane solution 200 ml was added, and then 0.5 mol / liter of the above dilithium polymerization initiator was added 230 ml. Was started.
　重合リアクターを５０℃に昇温しながら、１.５時間重合を行った後、１モル／リットルのエチレンオキシドのシクロヘキサン溶液を２５４ｍｌ添加し、更に２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、充分に乾燥させて、両末端が水酸基である２５℃において液状の液状ゴムを得た。 Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
　以上のようにして得られた液状ゴムは両末端ヒドロキシル基スチレン－ブタジエン共重合体（ＳＢ共重合体Ｂ）であり、結合スチレン含量が５５質量％であり、ブタジエン部分のビニル結合含量が６５％であった。また、数平均分子量が４０００、重量平均分子量が４８００、分子量分布が１.２０であった。 The liquid rubber obtained as described above is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer B) having a terminal styrene content of 55% by mass and a vinyl bond content of the butadiene portion of 65%. Met. The number average molecular weight was 4000, the weight average molecular weight was 4800, and the molecular weight distribution was 1.20.
　[製造例３：ＳＢ共重合体Ｃの合成例]
　充分に脱水精製したシクロヘキサン溶媒中に、１，３-(ジイソプロペニル)ベンゼン １モルを添加した後、トリエチルアミン ２モル、ｓｅｃ-ブチルリチウム ２モルを順次添加し、５０℃で２時間撹拌して、ジリチウム系重合開始剤を調製した。 [Production Example 3: Synthesis Example of SB Copolymer C]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a cyclohexane solvent that has been thoroughly dehydrated and purified, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added, followed by stirring at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared.
　アルゴン置換した７リットルの重合リアクターに、脱水精製したシクロヘキサンを１.４５ｋｇ、２２.９質量％の１，３-ブタジエンモノマーのヘキサン溶液を２.００ｋｇ、２０.０質量％のスチレンモノマーのシクロヘキサン溶液を０.７６５ｋｇ、１.１５モル／リットルの２，２-ビス(テトラヒドロフリル)プロパンのヘキサン溶液を２００ｍｌ添加した後、０.５モル／リットルの上記ジリチウム系重合開始剤を２２４ｍｌ添加して重合を開始させた。 In a 7 liter polymerization reactor purged with argon, 1.45 kg of dehydrated purified cyclohexane, 2.00 kg of hexane solution of 22.9% by mass of 1,3-butadiene monomer, and 20.0% by mass of cyclohexane solution of styrene monomer. 0.765 kg, 1.15 mol / liter of 2,2-bis (tetrahydrofuryl) propane in hexane solution (200 ml) was added, and 0.5 mol / liter of the above dilithium polymerization initiator was added (224 ml) for polymerization. Was started.
　重合リアクターを５０℃に昇温しながら、１.５時間重合を行った後、１モル／リットルのエチレンオキシドのシクロヘキサン溶液を２５４ｍｌ添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、充分に乾燥させて、両末端が水酸基である２５℃において液状の液状ゴムを得た。 Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
　以上のようにして得られた液状ゴムは両末端ヒドロキシル基スチレン－ブタジエン共重合体（ＳＢ共重合体Ｃ）であり、結合スチレン含量が２３質量％であり、ブタジエン部分のビニル結合含量が６５％であった。また、数平均分子量が４９００、重量平均分子量が６２００、分子量分布が１.２６であった。 The liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer C) with a terminal styrene content of 23% by mass and a vinyl bond content of the butadiene portion of 65%. Met. The number average molecular weight was 4,900, the weight average molecular weight was 6,200, and the molecular weight distribution was 1.26.
　[製造例４：ＳＢ共重合体Ｄの合成例]
　充分に脱水精製したシクロヘキサン溶媒中に、１，３－（ジイソプロペニル）ベンゼン１モルを添加した後、トリエチルアミン２モル、ｓｅｃ－ブチルリチウム２モルを順次添加し、５０℃で２時間攪拌して、ジリチウム系重合開始剤を調製した。 [Production Example 4: Synthesis Example of SB Copolymer D]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a fully dehydrated and purified cyclohexane solvent, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added, and the mixture is stirred at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared.
　アルゴン置換した７リットルの重合リアクターに、脱水精製したシクロヘキサンを１.５ｋｇ、２２.９質量％の１，３-ブタジエンモノマーのヘキサン溶液を１．６５ｋｇ、２０.０質量％のスチレンモノマーのシクロヘキサン溶液を１．００ｋｇ、１.１５モル／リットルの２，２-ビス(テトラヒドロフリル)プロパンのヘキサン溶液を３００ｍｌ添加した後、０.５モル／リットルの上記ジリチウム系重合開始剤を２３０ｍｌ添加して重合を開始させた。 In a 7-liter polymerization reactor purged with argon, 1.5 kg of dehydrated and purified cyclohexane, 1.65 kg of a hexane solution of 22.9% by mass of 1,3-butadiene monomer, and a cyclohexane solution of 20.0% by mass of styrene monomer 300 ml of a hexane solution of 1.00 kg, 1.15 mol / liter of 2,2-bis (tetrahydrofuryl) propane was added, and then 230 ml of the above dilithium polymerization initiator of 0.5 mol / liter was added for polymerization. Was started.
　重合リアクターを５０℃に昇温しながら、１.５時間重合を行った後、１モル／リットルのエチレンオキシドのシクロヘキサン溶液を２５４ｍｌ添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、充分に乾燥させて、両末端が水酸基である２５℃において液状の液状ゴムを得た。 Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 254 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
　以上のようにして得られた液状ゴムは両末端ヒドロキシル基スチレン－ブタジエン共重合体（ＳＢ共重合体Ｄ）であり、結合スチレン含量が３５質量％であり、ブタジエン部分のビニル結合含量が７８％であった。また、数平均分子量が４４００、重量平均分子量が５３００、分子量分布が１.２０であった。 The liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer D) with a terminal styrene content of 35% by mass and a vinyl bond content of the butadiene portion of 78%. Met. In addition, the number average molecular weight was 4,400, the weight average molecular weight was 5,300, and the molecular weight distribution was 1.20.
　[製造例５：ＳＢ共重合体Ｅの合成例]
　充分に脱水精製したシクロヘキサン溶媒中に、１，３－（ジイソプロペニル）ベンゼン１モルを添加した後、トリエチルアミン２モル、ｓｅｃ－ブチルリチウム２モルを順次添加し、５０℃で２時間攪拌して、ジリチウム系重合開始剤を調製した。 [Production Example 5: Synthesis example of SB copolymer E]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a fully dehydrated and purified cyclohexane solvent, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added, and the mixture is stirred at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared.
　アルゴン置換した７リットルの重合リアクターに、脱水精製したシクロヘキサンを１.９０ｋｇ、２２.９質量％の１，３-ブタジエンモノマーのヘキサン溶液を１．９０ｋｇ、２０.０質量％のスチレンモノマーのシクロヘキサン溶液を０．９００ｋｇ、１.６モル／リットルの２，２-ビス(テトラヒドロフリル)プロパンのヘキサン溶液を１３０．４ｍｌ添加した後、０.５モル／リットルの上記ジリチウム系重合開始剤を１０８．０ｍｌ添加して重合を開始させた。 In a 7 liter polymerization reactor purged with argon, 1.90 kg of dehydrated purified cyclohexane, 1.90 kg of hexane solution of 22.9% by mass of 1,3-butadiene monomer, and 20.0% by mass of cyclohexane solution of styrene monomer 0.900 kg, 1.6 mol / liter of 2,2-bis (tetrahydrofuryl) propane hexane solution 130.4 ml, and 0.5 mol / liter of the above dilithium polymerization initiator 108.0 ml. Polymerization was initiated by addition.
　重合リアクターを５０℃に昇温しながら、１.５時間重合を行った後、１モル／リットルのエチレンオキシドのシクロヘキサン溶液を１０８．０ｍｌ添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、充分に乾燥させて、両末端が水酸基である２５℃において液状の液状ゴムを得た。 Polymerization is carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., 108.0 ml of a 1 mol / liter ethylene oxide cyclohexane solution is added, and further stirred for 2 hours, and then 50 ml of isopropyl alcohol is added. did. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
　以上のようにして得られた光硬化性液状ゴムは両末端ヒドロキシル基スチレン－ブタジエン共重合体（ＳＢ共重合体Ｅ）であり、結合スチレン含量が２９質量％であり、ブタジエン部分のビニル結合含量が６５％であった。また、数平均分子量が１２，５００、重量平均分子量が１６，０００、分子量分布が１.２６であった。 The photocurable liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer E) having a terminal styrene content of 29% by mass and a vinyl bond content in the butadiene portion. Was 65%. The number average molecular weight was 12,500, the weight average molecular weight was 16,000, and the molecular weight distribution was 1.26.
　[製造例６：ＳＢ共重合体Ｆの合成例]
　充分に脱水精製したシクロヘキサン溶媒中に、１，３－（ジイソプロペニル）ベンゼン１モルを添加した後、トリエチルアミン２モル、ｓｅｃ－ブチルリチウム２モルを順次添加し、５０℃で２時間攪拌して、ジリチウム系重合開始剤を調製した。 [Production Example 6: Synthesis example of SB copolymer F]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a fully dehydrated and purified cyclohexane solvent, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added, and the mixture is stirred at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared.
　アルゴン置換した７リットルの重合リアクターに、脱水精製したシクロヘキサンを２．２０ｋｇ、２２.９質量％の１，３-ブタジエンモノマーのヘキサン溶液を１．８５ｋｇ、２０.０質量％のスチレンモノマーのシクロヘキサン溶液を１．１５ｋｇ、１.６モル／リットルの２，２-ビス(テトラヒドロフリル)プロパンのヘキサン溶液を１３０．４ｍｌ添加した後、０.５モル／リットルの上記ジリチウム系重合開始剤を７０ｍｌ添加して重合を開始させた。 In a 7 liter polymerization reactor purged with argon, 2.20 kg of dehydrated and purified cyclohexane, 1.85 kg of a hexane solution of 22.9% by mass of 1,3-butadiene monomer, and a cyclohexane solution of 20.0% by mass of styrene monomer After adding 130.4 ml of a hexane solution of 1.15 kg, 1.6 mol / liter of 2,2-bis (tetrahydrofuryl) propane, 70 ml of the above dilithium polymerization initiator of 0.5 mol / liter was added. Polymerization was started.
　重合リアクターを５０℃に昇温しながら、１.５時間重合を行った後、１モル／リットルのエチレンオキシドのシクロヘキサン溶液を７０ｍｌ添加し、さらに２時間撹拌した後、５０ｍｌのイソプロピルアルコールを添加した。重合体のヘキサン溶液をイソプロピルアルコール中に沈殿させ、充分に乾燥させて、両末端が水酸基である２５℃において液状の液状ゴムを得た。 Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., then 70 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and after further stirring for 2 hours, 50 ml of isopropyl alcohol was added. A hexane solution of the polymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a liquid rubber at 25 ° C. in which both ends are hydroxyl groups.
　以上のようにして得られた光硬化性液状ゴムは両末端ヒドロキシル基スチレン－ブタジエン共重合体（ＳＢ共重合体Ｆ）であり、結合スチレン含量が３５質量％であり、ブタジエン部分のビニル結合含量が６０％であった。また、数平均分子量が１７，２００、重量平均分子量が２１，５００、分子量分布が１.２５であった。 The photocurable liquid rubber thus obtained is a hydroxyl-terminated styrene-butadiene copolymer (SB copolymer F) having a terminal styrene content of 35% by mass, and a vinyl bond content in the butadiene portion. Was 60%. The number average molecular weight was 17,200, the weight average molecular weight was 21,500, and the molecular weight distribution was 1.25.
　＜ゴム組成物の調製及び評価＞
　上記のようにして合成したスチレン－ブタジエン共重合体又は市販のジエン系ポリマーを用いて、表１～５に示す配合のゴム組成物を調製し、下記の方法で、硬化性及び相溶性を評価した。 <Preparation and evaluation of rubber composition>
Using the styrene-butadiene copolymer synthesized as described above or a commercially available diene polymer, rubber compositions having the compositions shown in Tables 1 to 5 were prepared, and the curability and compatibility were evaluated by the following methods. did.
　《光硬化性の評価》
　イルガキュア１８４Ｄ（チバスペシャルティーケミカルズ社製、１－ヒドロキシシクロヘキシルフェニルケトン）を液状ゴム１００質量部に対して１質量部配合し、紫外線を７０００ｍＪ／ｃｍ2照射した後、２３℃において、組成物の硬化性を触診により評価した。溶液時と比較して完全に固体として硬化した場合を○、若干硬化した場合を△、全くしなかった場合を×とした。結果を表１～５に示す。 << Evaluation of photocurability >>
Irgacure 184D (manufactured by Ciba Specialty Chemicals, 1-hydroxycyclohexyl phenyl ketone) is blended in an amount of 1 part by mass with respect to 100 parts by mass of liquid rubber, irradiated with 7000 mJ / cm 2 of ultraviolet rays, and then cured at 23 ° C. Sex was assessed by palpation. The case where it was hardened completely as a solid as compared with the solution was indicated as ◯, the case where it was slightly cured as Δ, and the case where it was not cured at all as ×. The results are shown in Tables 1-5.
　《熱硬化性の評価》
　トリゴノックス１２１（アクゾ社製、ｔ-アミルパーオキシ-２-エチルヘキサノエート）を液状ゴム１００質量部に対して５質量部配合し、１５０℃で１０分間硬化させた。この際における組成物の硬化性を触診により評価し、溶液時と比較して完全に固体として硬化した場合を○、若干硬化した場合を△、全くしなかった場合を×とした。結果を表１～５に示す。 <Evaluation of thermosetting>
Trigonox 121 (manufactured by Akzo, t-amylperoxy-2-ethylhexanoate) was blended in an amount of 5 parts by mass with respect to 100 parts by mass of the liquid rubber and cured at 150 ° C. for 10 minutes. The curability of the composition at this time was evaluated by palpation. The case where it was completely cured as compared with the solution was evaluated as ◯, the case where it was slightly cured as Δ, and the case where it did not at all as ×. The results are shown in Tables 1-5.
　《相溶性の評価》
　各成分を配合した後、得られた組成物を透明ガラス基板上に塗布し、目視にて評価した。評価基準を以下に示す。
　　○　：透明
　　○△：若干白濁
　　△　：白濁
　　△×：やや相分離
　　×　：完全に相分離或いは溶解せず
　結果を表１～５に示す。 << Evaluation of compatibility >>
After blending each component, the obtained composition was applied on a transparent glass substrate and visually evaluated. The evaluation criteria are shown below.
○: Transparent ○ △: Slightly cloudy △: White turbidity Δ ×: Slight phase separation ×: Phase separation or incomplete dissolution The results are shown in Tables 1 to 5.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
※１：Ｒｉｃｏｎ１００、サートマー社製、数平均分子量＝４２００、結合スチレン含量＝２５質量％、ブタジエン部分のビニル結合含量＝６０％、末端官能基：無し、２５℃において液状
※２：Ｒｉｃｏｎ１８１、サートマー社製、数平均分子量＝３２００、結合スチレン含量＝２５質量％、ブタジエン部分のビニル結合含量＝３０％、末端官能基：無し、２５℃において液状
※３：ＳＢ共重合体Ａ、上記の方法で合成、数平均分子量＝５２００、結合スチレン含量＝３５質量％、ブタジエン部分のビニル結合含量＝６５％、末端官能基：ＯＨ、２５℃において液状
※４：ＳＢ共重合体Ｂ、上記の方法で合成、数平均分子量＝４０００、結合スチレン含量＝５５質量％、ブタジエン部分のビニル結合含量＝６５％、末端官能基：ＯＨ、２５℃において液状
※５：ＳＢ共重合体Ｃ、上記の方法で合成、数平均分子量＝４９００、結合スチレン含量＝２３質量％、ブタジエン部分のビニル結合含量＝６５％、末端官能基：ＯＨ、２５℃において液状
※６：ＳＢ共重合体Ｄ、数平均分子量＝４４００、結合スチレン含量＝３５質量％、ブタジエン部分のビニル結合含量＝７８％、末端官能基：ＯＨ、２５℃において液状
※７：ＳＢ共重合体Ｅ、数平均分子量＝１２５００、結合スチレン含量＝２９質量％、ブタジエン部分のビニル結合含量＝６５％、末端官能基：ＯＨ、２５℃において液状
※８：ＳＢ共重合体Ｆ、数平均分子量＝１７２００、結合スチレン含量＝３５質量％、ブタジエン部分のビニル結合含量＝６０％、末端官能基：ＯＨ、２５℃において液状
※９：Ｐｏｌｙ－ＩＰ（イソプレンゴム、ホモポリマー）、出光興産製、数平均分子量＝２５００、末端官能基：ＯＨ、２５℃において液状のポリイソプレン
※１０：Ｐｏｌｙ－ｂｄ　Ｒ－１５ＨＴ(ブタジエンゴム、１，４－ポリブタジエン構造)、出光興産製、数平均分子量＝１２００、末端官能基：ＯＨ
※１１：ＬＩＲ－３０（イソプレンゴム、ホモポリマー）、(株)クラレ製、数平均分子量＝２８０００、末端官能基：なし
※１２：ＬＩＲ－５０（イソプレンゴム、ホモポリマー）、(株)クラレ製、数平均分子量＝５４０００、末端官能基：なし
※１３：ＬＩＲ－３００（ブタジエンゴム、１，４－ポリブタジエン構造）、(株)クラレ製、数平均分子量＝４４０００、末端官能基：なし
※１４：ＬＩＲ－４０３（イソプレンゴム、官能基含有ホモポリマー）、(株)クラレ製、数平均分子量＝３４０００、末端官能基：無水マレイン酸
※１５：Ｒｉｃｏｎ１４２（ブタジエンゴム、１，４－ポリブタジエン構造）、サートマー社製、数平均分子量＝３９００、結合スチレン含量＝０質量％、ブタジエン部分のビニル結合含量＝５５％、末端官能基：なし、２５℃において液状のポリブタジエン
※１６：Ｒｉｃｏｎ１５０（ブタジエンゴム、１，４－ポリブタジエン構造）、サートマー社製、数平均分子量＝３９００、ブタジエン部分のビニル結合含量＝７０％、末端官能基：なし
※１７：Ｒｉｃｏｎ１３４（ブタジエンゴム、１，４－ポリブタジエン構造）、サートマー社製、数平均分子量＝８０００、ブタジエン部分のビニル結合含量＝２８％、末端官能基：なし
※１８：Ｒｉｃｏｎ１５４（ブタジエンゴム、１，３－ブタジエンホモポリマー）、サートマー社製、数平均分子量＝５２００、末端官能基：なし
※１９：ＴＭＭＰ、トリメチロールプロパントリス(３-メルカプトプロピオネート)
※２０：ＴＥＭＰＩＣ、トリス[(３-メルカプトプロピオニロキシ)-エチル]イソシアヌレート
※２１：ＰＥＭＰ、ペンタエリスリトールテトラキス(３-メルカプトプロピオネート)
※２２：ＤＰＭＰ、ジペンタエリスリトールヘキサキス(３-メルカプトプロピオネート)
※２３：ＰＥ１、ペンタエリスリトールテトラキス(３-メルカプトブチレート)
※２４：ＥＧＭＰ－４、テトラエチレングリコールビス(３-メルカプトプロピオネート)
※２５：ジスネットＦ、三協化成(株)製 * 1: Ricon 100, manufactured by Sartomer, number average molecular weight = 4200, bound styrene content = 25 mass%, vinyl bond content of butadiene moiety = 60%, terminal functional group: none, liquid at 25 ° C. * 2: Ricon 181, Sartomer Manufactured, number average molecular weight = 3200, bound styrene content = 25 mass%, vinyl bond content of butadiene moiety = 30%, terminal functional group: none, liquid at 25 ° C. * 3: SB copolymer A, synthesized by the above method , Number average molecular weight = 5200, bound styrene content = 35 mass%, vinyl bond content of butadiene moiety = 65%, terminal functional group: OH, liquid at 25 ° C. * 4: SB copolymer B, synthesized by the above method, Number average molecular weight = 4000, bound styrene content = 55 mass%, vinyl bond content of butadiene moiety = 65%, terminal functional group: OH, 25 * 5: SB copolymer C, synthesized by the above method, number average molecular weight = 4900, bound styrene content = 23 mass%, vinyl bond content of butadiene moiety = 65%, terminal functional group: OH, at 25 ° C. Liquid * 6: SB copolymer D, number average molecular weight = 4400, bound styrene content = 35 mass%, vinyl bond content of butadiene moiety = 78%, terminal functional group: OH, liquid at 25 ° C. * 7: SB copolymer weight Compound E, number average molecular weight = 12,500, bound styrene content = 29% by mass, vinyl bond content of butadiene moiety = 65%, terminal functional group: OH, liquid at 25 ° C. * 8: SB copolymer F, number average molecular weight = 17200, bound styrene content = 35 mass%, vinyl bond content of butadiene moiety = 60%, terminal functional group: OH, liquid at 25 ° C. * 9: Poly-IP ( Soprene rubber, homopolymer), manufactured by Idemitsu Kosan, number average molecular weight = 2500, terminal functional group: OH, polyisoprene liquid at 25 ° C. * 10: Poly-bd R-15HT (butadiene rubber, 1,4-polybutadiene structure), Idemitsu Kosan, number average molecular weight = 1200, terminal functional group: OH
* 11: LIR-30 (isoprene rubber, homopolymer), manufactured by Kuraray Co., Ltd., number average molecular weight = 28000, terminal functional group: none * 12: LIR-50 (isoprene rubber, homopolymer), manufactured by Kuraray Co., Ltd. , Number average molecular weight = 54000, terminal functional group: none * 13: LIR-300 (butadiene rubber, 1,4-polybutadiene structure), manufactured by Kuraray Co., Ltd., number average molecular weight = 44000, terminal functional group: none * 14: LIR-403 (isoprene rubber, functional group-containing homopolymer), manufactured by Kuraray Co., Ltd., number average molecular weight = 34000, terminal functional group: maleic anhydride * 15: Ricon 142 (butadiene rubber, 1,4-polybutadiene structure), Sartomer Number average molecular weight = 3900, bound styrene content = 0 mass%, vinyl bond content of butadiene moiety = 55%, terminal functional group None, polybutadiene liquid at 25 ° C. * 16: Ricon 150 (butadiene rubber, 1,4-polybutadiene structure), manufactured by Sartomer, number average molecular weight = 3900, vinyl bond content of butadiene moiety = 70%, terminal functional group: none * 17: Ricon134 (butadiene rubber, 1,4-polybutadiene structure), manufactured by Sartomer, number average molecular weight = 8000, vinyl bond content of butadiene portion = 28%, terminal functional group: none * 18: Ricon154 (butadiene rubber, 1, 3-butadiene homopolymer), manufactured by Sartomer, number average molecular weight = 5200, terminal functional group: none * 19: TMMP, trimethylolpropane tris (3-mercaptopropionate)
* 20: TEMPIC, tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate * 21: PEMP, pentaerythritol tetrakis (3-mercaptopropionate)
* 22: DPMP, dipentaerythritol hexakis (3-mercaptopropionate)
* 23: PE1, pentaerythritol tetrakis (3-mercaptobutyrate)
* 24: EGMP-4, tetraethylene glycol bis (3-mercaptopropionate)
* 25: Gisnet F, Sankyo Kasei Co., Ltd.
　表１～５の結果によれば、２５℃において液状であるスチレン－ブタジエン共重合体（Ａ）とメルカプトカルボン酸由来のポリチオール（Ｂ）とを含む実施例１～２０は、スチレン－ブタジエン共重合体（Ａ）のみを含む比較例１、メルカプトカルボン酸由来でないポリチオールを用いた比較例２、およびスチレン－ブタジエン共重合体以外の液状ゴムを用いた比較例３～３５に比べ、相溶性が良好であり、光硬化性および熱硬化性ともに優れた効果を発揮することがわかる。 According to the results shown in Tables 1 to 5, Examples 1 to 20 containing a styrene-butadiene copolymer (A) that is liquid at 25 ° C. and a polythiol (B) derived from mercaptocarboxylic acid, Compared with Comparative Example 1 containing only the union (A), Comparative Example 2 using polythiol not derived from mercaptocarboxylic acid, and Comparative Examples 3 to 35 using liquid rubber other than styrene-butadiene copolymer, good compatibility It can be seen that both the photo-curing property and the thermo-curing effect are excellent.

Claims (6)

  1. 　２５℃において液状であるスチレン－ブタジエン共重合体（Ａ）と、
    　メルカプトカルボン酸由来のポリチオール（Ｂ）と
    を含むことを特徴とするチオール含有液状ゴム組成物。     A styrene-butadiene copolymer (A) which is liquid at 25 ° C .;
    A thiol-containing liquid rubber composition comprising a polythiol (B) derived from mercaptocarboxylic acid.
  2. 　前記スチレン－ブタジエン共重合体（Ａ）の結合スチレン含有量が、２０～９０質量％であることを特徴とする請求項１に記載のチオール含有液状ゴム組成物。 2. The thiol-containing liquid rubber composition according to claim 1, wherein the styrene-butadiene copolymer (A) has a bound styrene content of 20 to 90% by mass.
  3. 　前記スチレン－ブタジエン共重合体（Ａ）がランダム共重合体であることを特徴とする請求項１または２に記載のチオール含有液状ゴム組成物。 The thiol-containing liquid rubber composition according to claim 1 or 2, wherein the styrene-butadiene copolymer (A) is a random copolymer.
  4. 　前記ポリチオール（Ｂ）が、テトラエチレングリコールビス(３-メルカプトプロピオネート)、トリメチロールプロパントリス(３-メルカプトプロピオネート)、トリス[(３-メルカプトプロピオニロキシ)-エチル]イソシアヌレート、ペンタエリスリトールテトラキス(３-メルカプトプロピオネート)、ジペンタエリスリトールヘキサキス(３-メルカプトプロピオネート)、１，４-ビス(３-メルカプトブチリルオキシ)ブタン、ペンタエリスリトールテトラキス(３-メルカプトブチレート)、及び１，３，５-トリス(３-メルカプトブチルオキシエチル)-１，３，５-トリアジン-２，４，６(１Ｈ，３Ｈ，５Ｈ)-トリオンからなる群から選択される少なくとも一種であることを特徴とする請求項１～３のいずれかに記載のチオール含有液状ゴム組成物。 The polythiol (B) is tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate, penta Erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) And at least one selected from the group consisting of 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione The thiol-containing liquid rubber composition according to any one of claims 1 to 3, wherein the thiol-containing liquid rubber composition is provided.
  5. 　前記ポリチオール（Ｂ）の含有量が、スチレン－ブタジエン共重合体（Ａ）１００重量部に対して、４０質量部以下であることを特徴とする請求項１～４のいずれかに記載のチオール含有液状ゴム組成物。 The thiol-containing product according to any one of claims 1 to 4, wherein the content of the polythiol (B) is 40 parts by mass or less with respect to 100 parts by weight of the styrene-butadiene copolymer (A). Liquid rubber composition.
  6. 　前記スチレン－ブタジエン共重合体（Ａ）の数平均分子量（Ｍｎ）が、１２００～４００００であることを特徴とする請求項１～５のいずれかに記載のチオール含有液状ゴム組成物。 The thiol-containing liquid rubber composition according to any one of claims 1 to 5, wherein the styrene-butadiene copolymer (A) has a number average molecular weight (Mn) of 1200 to 40000.
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JP2015063648A (en) * 2013-08-26 2015-04-09 横浜ゴム株式会社 Rubber composition and pneumatic tire made using the same
JP2015524492A (en) * 2012-07-09 2015-08-24 ランクセス・ドイチュランド・ゲーエムベーハー Silica-containing rubber mixture containing polyhydric alcohol ω-mercaptocarboxylic acid ester
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JP2015524492A (en) * 2012-07-09 2015-08-24 ランクセス・ドイチュランド・ゲーエムベーハー Silica-containing rubber mixture containing polyhydric alcohol ω-mercaptocarboxylic acid ester
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JP5653344B2 (en) 2015-01-14
US20120041154A1 (en) 2012-02-16
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JPWO2010119708A1 (en) 2012-10-22

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